WO2012124222A1 - アルミニウムケイ酸塩、金属イオン吸着剤及びそれらの製造方法 - Google Patents

アルミニウムケイ酸塩、金属イオン吸着剤及びそれらの製造方法 Download PDF

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WO2012124222A1
WO2012124222A1 PCT/JP2011/078349 JP2011078349W WO2012124222A1 WO 2012124222 A1 WO2012124222 A1 WO 2012124222A1 JP 2011078349 W JP2011078349 W JP 2011078349W WO 2012124222 A1 WO2012124222 A1 WO 2012124222A1
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aluminum silicate
aluminum
ppm
peak
ions
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PCT/JP2011/078349
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English (en)
French (fr)
Japanese (ja)
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紘輝 三國
潔 川合
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日立化成工業株式会社
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Priority to US14/004,581 priority Critical patent/US9782749B2/en
Priority to EP11861291.0A priority patent/EP2684847B1/en
Priority to KR1020137025289A priority patent/KR101907048B1/ko
Priority to JP2013504521A priority patent/JP5958461B2/ja
Priority to CN201180069225.7A priority patent/CN103635426B/zh
Publication of WO2012124222A1 publication Critical patent/WO2012124222A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • Japanese Patent Application Laid-Open No. 2003-334543 discloses a mixture comprising fibrous activated carbon, a fine inorganic compound having a particle size of 0.1 ⁇ m to 90 ⁇ m having heavy metal adsorption performance, and a binder.
  • An activated carbon molded body is disclosed.
  • an aluminosilicate zeolite is used as the fine particle inorganic compound.
  • JP 2000 -342926 discloses a heavy metal adsorbent in which a chelate-forming group-containing compound is bound to one or more porous materials selected from the group consisting of activated carbon, zeolite, diatomaceous earth, natural sand and ceramics. Yes.
  • an object of the present invention is to provide an aluminum silicate excellent in metal ion adsorption, a metal ion adsorbent containing the aluminum silicate as a component, and a method for producing them.
  • Element ratio Si / Al Si / Al is a molar ratio of 0.3 to 1.0, has a peak in the vicinity of 3 ppm in the 27 Al-NMR spectrum, and has a peak in the vicinity of ⁇ 78 ppm in the 29 Si-NMR spectrum.
  • An aluminum silicate having an area ratio (peak B / peak A) between a peak A in the vicinity and a peak B in the vicinity of ⁇ 85 ppm is 2.0 to 9.0.
  • Si / Al element ratio Si / Al is 0.3 to 1.0 in molar ratio
  • 27 Al-NMR spectrum has a peak around 3 ppm
  • 29 Si-NMR spectrum is around -78 ppm
  • Transmission electron microscope (TEM) photograph having a peak near ⁇ 85 ppm
  • the aluminum silicate does not have a tubular product having a length of 50 nm or more when observed at a magnification of 100,000.
  • ⁇ 3> The aluminum silicate according to ⁇ 1>, wherein a tubular product having a length of 50 nm or more does not exist when observed at a magnification of 100,000 in a transmission electron microscope (TEM) photograph.
  • TEM transmission electron microscope
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the BET specific surface area is 250 m 2 / g or more, the total pore volume is 0.1 cm 3 / g or more, and the average pore diameter is 1.5 nm or more.
  • the aluminum silicate according to any one of the above.
  • the aluminum silicate has an area ratio (peak B / peak A) between peak A near ⁇ 78 ppm and peak B near ⁇ 85 ppm in the 29 Si-NMR spectrum of 2.0 to 9.0. It is a metal ion adsorbent as described in ⁇ 6> above.
  • the aluminum silicate has a BET specific surface area of 250 m 2 / g or more, a total pore volume of 0.1 cm 3 / g or more, and an average pore diameter of 1.5 nm or more.
  • ⁇ 12> (a) a step of obtaining a reaction product by mixing a solution containing silicate ions and a solution containing aluminum ions, (b) a step of desalting and solid-separating the reaction product, and (c) ) A step of subjecting the solid separated in the step (b) to a heat treatment in an aqueous medium in the presence of an acid under a concentration condition in which the silicon atom concentration is 100 mmol / L or more and the aluminum atom concentration is 100 mmol / L or more; (D) The aluminum silicate according to any one of ⁇ 1> to ⁇ 5>, further comprising a step of desalting and solid-separating the product obtained by the heat treatment in the step (c). It is a manufacturing method.
  • the solid separated in the step (b) has an electrical conductivity of 4.0 S / m or less when dispersed in water so that the concentration is 60 g / L. It is a manufacturing method of aluminum silicate.
  • step (c) the pH is adjusted to 3 or more and less than 7, and the heat treatment is performed at a temperature of 80 ° C. to 160 ° C. for 96 hours or less. It is a manufacturing method of aluminum silicate.
  • the silicon atom concentration of the solution containing the silicate ions is 100 mmol / L or more
  • the aluminum atom concentration of the solution containing the aluminum ions is 100 mmol / L or more
  • silicon with respect to aluminum The method for producing an aluminum silicate according to any one of ⁇ 12> to ⁇ 14>, wherein the element ratio Si / Al is mixed so that the molar ratio is 0.3 to 1.0. is there.
  • the step (b) includes a step of dispersing the reaction product in an aqueous medium to obtain a dispersion, and a step of adjusting the pH of the dispersion to 5 to 7 and performing solid separation.
  • ⁇ 17> (a) a step of mixing a solution containing silicate ions and a solution containing aluminum ions to obtain a reaction product, (b) a step of desalting and separating the reaction product, and (c) ) A step of subjecting the solid separated in the step (b) to a heat treatment in an aqueous medium in the presence of an acid; and (d) a step obtained by the heat treatment in the step (c).
  • the solid separated in the step (b) has an electric conductivity of 4.0 S / m or less when dispersed in water so that the concentration is 60 g / L. ⁇ 17> or ⁇ 18>.
  • the step (c) is a step in which the pH is adjusted to 3 or more and less than 7, and the heat treatment is performed at a temperature of 80 ° C. to 160 ° C. for 96 hours or less.
  • the silicon atom concentration of the solution containing the silicate ions is 100 mmol / L or more
  • the aluminum atom concentration of the solution containing the aluminum ions is 100 mmol / L or more
  • silicon with respect to aluminum ⁇ 17> to ⁇ 20> which is a step of mixing the solution containing silicate ions and the solution containing aluminum ions so that the element ratio Si / Al in the molar ratio is 0.3 to 1.0. It is a manufacturing method of the metal ion adsorbent of any one.
  • the step (b) includes a step of dispersing the reaction product in an aqueous medium to obtain a dispersion, and a step of adjusting the pH of the dispersion to 5 to 7 and performing solid separation.
  • an aluminum silicate having an excellent metal ion adsorptivity, a metal ion adsorbent containing the aluminum silicate as a component, and a production method thereof.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
  • the aluminum silicate according to the first embodiment of the present invention has a Si / Al element ratio of Si / Al of 0.3 to 1.0 in molar ratio, and has a peak around 3 ppm in the 27 Al-NMR spectrum.
  • Peak B / peak A The area ratio (peak B / peak A) between the peak A around ⁇ 78 ppm and the peak B around ⁇ 85 ppm in the 29 Si-NMR spectrum is 2.0 to 9.0, or the transmission type It is an aluminum silicate in which a tubular object having a length of 50 nm or more does not exist when observed at a magnification of 100,000 in an electron microscope (TEM) photograph.
  • Powder X-ray diffraction is performed using CuK ⁇ rays as an X-ray source.
  • a powder X-ray diffractometer manufactured by Rigaku Corporation: Geigerflex RAD-2X (trade name) can be used.
  • FIG. 1 shows a powder X-ray diffraction spectrum of aluminum silicate according to Production Example 1 described later as an example of the aluminum silicate of the first embodiment.
  • FIG. 1 also shows a powder X-ray diffraction spectrum of aluminum silicate according to Production Example 2 called so-called imogolite.
  • precipitation of aluminum hydroxide can be suppressed by making the heating temperature at the time of heat processing into 160 degrees C or less.
  • content of aluminum hydroxide can be adjusted by adjusting pH at the time of the desalting process by centrifugation.
  • the aluminum silicate of the first embodiment has an Si / Al element ratio of Si / Al of 0.3 to 1.0 in terms of molar ratio from the viewpoint of improving the adsorption ability of metal ions, and 0.4 Is preferably 0.6, more preferably 0.45 to 0.55.
  • Si / Al molar ratio is less than 0.3, the amount of Al that does not contribute to the improvement of the aluminum silicate adsorption capacity becomes excessive, and when it exceeds 1.0, the aluminum silicate adsorption capacity is improved.
  • the amount of Si that does not contribute tends to be excessive.
  • the element ratio Si / Al of Si and Al can be measured by an ordinary method using an ICP emission spectrometer (for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.).
  • ICP emission spectrometer for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.
  • the aluminum silicate of the first embodiment has a peak in the vicinity of 3 ppm in the 27 Al-NMR spectrum.
  • the 27 Al-NMR measurement apparatus for example, AV400WB type manufactured by Bruker BioSpin can be used, and specific measurement conditions are as follows.
  • Resonance frequency 104MHz
  • Measuring method MAS (single pulse)
  • MAS rotation speed 10 kHz
  • Measurement area 52 kHz
  • Number of data points 4096 resolution (measurement area / number of data points): 12.7 Hz
  • Pulse width 3.0 ⁇ sec
  • Delay time 2 seconds
  • Chemical shift value standard 3.94 ppm of ⁇ -alumina window function: exponential function Line Broadening coefficient: 10 Hz
  • FIG. 2 shows a 27 Al-NMR spectrum of an aluminum silicate according to Production Example 1 described later as an example of the aluminum silicate of the first embodiment.
  • FIG. 2 also shows a 27 Al-NMR spectrum of an aluminum silicate according to Production Example 2 called so-called imogolite.
  • the aluminum silicate of the first embodiment has a peak in the vicinity of 3 ppm in the 27 Al-NMR spectrum.
  • the peak around 3 ppm is estimated to be a peak derived from 6-coordinated Al.
  • the peak near 55 ppm is estimated to be a peak derived from tetracoordinated Al.
  • the area ratio of the peak near 55 ppm to the peak near 3 ppm in the 27 Al-NMR spectrum is preferably 25% or less, more preferably 20% or less. Preferably, it is more preferably 15% or less.
  • the specific aluminum silicate according to the first embodiment has an area ratio of a peak near 55 pm to a peak near 3 ppm in the 27Al-NMR spectrum of 1% or more from the viewpoint of metal ion adsorption and metal ion selectivity. Preferably, it is 5% or more, more preferably 10% or more.
  • the aluminum silicate of the first embodiment has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29 Si-NMR spectrum.
  • the 29 Si-NMR measurement apparatus for example, AV400WB type manufactured by Bruker BioSpin can be used, and specific measurement conditions are as follows.
  • Resonance frequency 79.5 MHz
  • Measuring method MAS (single pulse)
  • MAS rotation speed 6 kHz
  • Measurement area 24 kHz
  • Number of data points 2048 resolution (measurement area / number of data points): 5.8 Hz
  • Pulse width 4.7 ⁇ sec
  • Delay time 600 sec chemical shift value criterion: TMSP-d 4 (3- (trimethylsilyl) (2,2,3,3- 2 H 4) propionate) 1.52Ppm
  • the window function exponential function Line Broadening coefficient: 50 Hz
  • FIG. 3 shows a 29 Si-NMR spectrum of an aluminum silicate according to Production Example 1 described later as an example of the aluminum silicate of the first embodiment.
  • FIG. 3 also shows a 29 Si-NMR spectrum of the aluminum silicate according to Production Example 2 called so-called imogolite.
  • the aluminum silicate of the first embodiment has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29 Si-NMR spectrum.
  • the peak A that appears in the vicinity of ⁇ 78 ppm is attributed to the structure of HO—Si— (OAl) 3 derived from an aluminum silicate having a crystal structure such as imogolite and allophanes.
  • the peak B appearing around ⁇ 85 ppm is considered to be an aluminum silicate having a viscosity structure or an aluminum silicate having an amorphous structure. Therefore, the aluminum silicate of the first embodiment is presumed to be a mixture or composite of an aluminum silicate having a crystal structure and an aluminum silicate having a viscosity structure or an amorphous structure.
  • the aluminum silicate of the first embodiment has an area ratio (peak B / peak A) between peak A near -78 ppm and peak B near -85 ppm in the 29 Si-NMR spectrum of 2.0 to 9.0, or a tube having a length of 50 nm or more does not exist when observed at a magnification of 100,000 in a transmission electron microscope (TEM) photograph.
  • TEM transmission electron microscope
  • the area of peak A near ⁇ 78 ppm is the area of the region surrounded by the straight line passing through ⁇ 81 ppm and the base line perpendicular to the chemical shift axis, and the area of peak B is orthogonal to the chemical shift axis.
  • require the area of each said peak with the analysis software integrated in the NMR measuring apparatus.
  • the area ratio of peak B / peak A obtained from the areas of peaks A and B obtained above is 2.0 to 9.0 from the viewpoint of improving metal ion adsorption ability, and is 2.0 to 7. 0 is preferable, 2.0 to 5.0 is more preferable, and 2.0 to 4.0 is still more preferable.
  • imogolite fibers which are tubular aluminum silicates
  • TEM transmission electron microscope
  • FIG. 4 shows an example of a transmission electron microscope (TEM) photograph of aluminum silicate.
  • the aluminum silicate shown in FIG. 4 is an aluminum silicate according to Production Example 1 described later.
  • FIG. 5 shows a transmission electron microscope (TEM) photograph of aluminum silicate according to Production Example 2 which is tubular aluminum silicate and is called so-called imogolite.
  • TEM transmission electron microscope
  • Observation of aluminum silicate with a transmission electron microscope (TEM) is performed at an acceleration voltage of 100 kV.
  • TEM transmission electron microscope
  • a solution after heating before the second washing step (desalting and solid separation) in the manufacturing method described later is dropped on a support for preparing a TEM observation sample, and then dried to form a thin film.
  • an observation sample is prepared using an appropriately diluted solution after the heat treatment so that a sufficient contrast can be obtained.
  • the aluminum silicate of the first embodiment preferably has a BET specific surface area of 200 m 2 / g or more, more preferably 250 m 2 / g or more, from the viewpoint of improving the adsorption ability of metal ions. More preferably, it is 2 / g or more.
  • the upper limit of the BET specific surface area is not particularly limited, but a part of Si and Al in the aluminum silicate is bonded in the form of Si—O—Al, which contributes to the improvement of the metal ion adsorption capacity.
  • the BET specific surface area is preferably 1500 m 2 / g or less, more preferably 1200 m 2 / g or less, and still more preferably 1000 m 2 / g or less.
  • the BET specific surface area of aluminum silicate is measured from nitrogen adsorption capacity according to JIS Z 8830.
  • the evaluation apparatus for example, AUTOSORB-1 (trade name) manufactured by QUANTACHROME can be used.
  • AUTOSORB-1 trade name manufactured by QUANTACHROME
  • pretreatment for removing moisture by heating is first performed.
  • the measurement cell charged with 0.05 g of the measurement sample is depressurized to 10 Pa or less with a vacuum pump, heated at 110 ° C., held for 3 hours or more, and kept at a normal temperature while maintaining the depressurized state. Cool naturally to (25 ° C).
  • the evaluation temperature is 77K
  • the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • Aluminum silicate in the first embodiment from the viewpoint of improving the adsorption capacity of the metal ion is preferably the total pore volume is 0.1 cm 3 / g or more, it is 0.12 cm 3 / g or more Is more preferably 0.15 cm 3 / g or more.
  • the upper limit of the total pore volume is not particularly limited, but a part of Si and Al in the aluminum silicate bonds in the form of Si-O-Al, which contributes to the improvement of metal ion adsorption capacity. From the viewpoint that the total pore volume is, it is preferable that the total pore volume is 1.5 cm 3 / g or less, more preferably 1.2 cm 3 / g or less, and 1.0 cm 3 / g or less. Is more preferable.
  • the total pore volume of aluminum silicate is based on the BET specific surface area, and the gas adsorption amount closest to relative pressure 1 is converted to liquid among the data obtained when the relative pressure is 0.95 or more and less than 1. And ask.
  • the aluminum silicate of the first embodiment preferably has an average pore diameter of 1.5 nm or more, more preferably 1.7 nm or more, from the viewpoint of improving the ability to adsorb metal ions. More preferably, it is 0 nm or more.
  • the upper limit of the total pore volume is preferably 50 nm or less, more preferably 20 nm or less, and further preferably 5.0 nm or less, from the viewpoint of improving the adsorption ability of metal ions.
  • the average pore diameter of aluminum silicate is determined on the basis of the BET specific surface area and the total pore volume, assuming that all the pores are composed of one cylindrical pore.
  • the aluminum silicate which is 1st embodiment of this invention can be manufactured with the following manufacturing methods.
  • the method for producing an aluminum silicate of the present invention includes (a) a step of mixing a solution containing silicate ions and a solution containing aluminum ions to obtain a reaction product, and (b) desalting the reaction product. And (c) in the presence of an acid, the silicon atom concentration is 100 mmol / L or more and the aluminum atom concentration is 100 mmol / L or more in the presence of an acid.
  • the metal ions After desalting the coexisting ions from the solution containing the reaction product of silicate ions and aluminum ions, the metal ions are treated by heating in the presence of an acid in a higher concentration condition than when producing so-called imogolite.
  • Aluminum silicate having excellent adsorption ability can be produced efficiently. This can be considered as follows, for example. In general, when a heat treatment in the presence of an aluminum silicate acid is carried out with a dilute solution, a tubular aluminum silicate having a continuous regular structure is formed. However, under high concentration conditions such as the production method of the present invention, it is considered that an aluminum silicate having a clay structure and an amorphous structure in addition to a regular partial structure is formed.
  • Step of obtaining a reaction product In the step of obtaining a reaction product, a solution containing silicate ions and a solution containing aluminum ions are mixed to mix aluminum silicate as a reaction product and coexisting ions. Obtain a solution.
  • silicate ion and aluminum ion When synthesizing aluminum silicate, silicate ions and aluminum ions are required as raw materials.
  • the silicic acid source constituting the solution containing silicate ions (hereinafter also referred to as “silicate solution”) is not particularly limited as long as silicate ions are generated when solvated. Examples thereof include, but are not limited to, tetraalkoxysilanes such as sodium orthosilicate, sodium metasilicate, and tetraethoxysilane.
  • the aluminum source which comprises the solution containing aluminum ion will not be restrict
  • a material that can easily be solvated with the silicate source and the aluminum source as raw materials can be appropriately selected and used.
  • water, ethanol or the like can be used. It is preferable to use water from the viewpoint of reducing the coexisting ions in the solution during the heat treatment and ease of handling.
  • the silicon atom concentration of the silicic acid solution is not particularly limited.
  • the silicon atom concentration of the silicic acid solution which is preferably 100 mmol / L to 1000 mmol / L, is 100 mmol / L or more, productivity is improved and aluminum silicate can be produced efficiently. Moreover, productivity improves more according to the silicon atom concentration of a silicic acid solution as the silicon atom concentration of a silicic acid solution is 1000 mmol / L or less.
  • the aluminum atom concentration of the aluminum solution is not particularly limited. Preferably, it is 100 mmol / L to 1000 mmol / L. When the aluminum atom concentration of the aluminum solution is 100 mmol / L or more, productivity is improved, and aluminum silicate can be produced efficiently. Further, when the aluminum atom concentration of the aluminum solution is 1000 mmol / L or less, the productivity is further improved according to the aluminum atom concentration of the aluminum solution.
  • a solution containing silicate ions and a solution containing aluminum ions are mixed to produce an aluminum silicate containing coexisting ions as a reaction product, and then the aluminum silicate containing the coexisting ions is desalted and solid
  • a first cleaning step for separation is performed.
  • the first washing step at least a part of the coexisting ions is removed from the mixed solution to reduce the coexisting ion concentration in the mixed solution.
  • desalting and solid separation include anions other than silicate ions derived from a silicate source and an aluminum source (for example, chloride ions and nitrate ions) and cations other than aluminum ions (for example, sodium ions).
  • anions other than silicate ions derived from a silicate source and an aluminum source for example, chloride ions and nitrate ions
  • cations other than aluminum ions for example, sodium ions
  • the first washing step is preferably performed so that the concentration of coexisting ions is not more than a predetermined concentration.
  • the electrical conductivity of the dispersion is 4.0 S / m. It is preferable to carry out so that it is less than or equal to 1.0 mS / m or more and 3.0 S / m or less, more preferably 1.0 mS / m or more and 2.0 S / m or less. Is more preferable.
  • the electrical conductivity of the dispersion is 4.0 S / m or less, the desired aluminum silicate tends to be more easily formed in the synthesis step.
  • the electrical conductivity is measured at normal temperature (25 ° C.) using FORI 55 manufactured by HORIBA Co., Ltd. and 9382-10D, a general electrical conductivity cell manufactured by HORIBA.
  • the first washing step includes a step of dispersing the aluminum silicate in an aqueous medium to obtain a dispersion, and a step of adjusting the pH of the dispersion to 5 to 7 to precipitate aluminum silicate.
  • cleaning process using centrifugation it can carry out as follows.
  • the pH is adjusted to 5-7 by adding alkali or the like to the mixed solution.
  • the supernatant solution is discharged and the solid is separated as a gel-like precipitate.
  • the separated solid is redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 7, but preferably 5.5 to 6.8, and more preferably 5.8 to 6.5.
  • the alkali used for pH adjustment is not particularly limited. For example, sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and its standard rotor NA-16, it can be set at 3000 rpm (1450 G) or more for 5 to 10 minutes at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of the reduction of coexisting ions and ease of handling, water is preferably used, and pure water is more preferably used. It should be noted that pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the first washing step may be appropriately set according to the remaining amount of coexisting ions. For example, it can be 1 to 6 times. If the washing is repeated about three times, the residual amount of coexisting ions is reduced to such an extent that does not affect the synthesis of the desired aluminum silicate.
  • PH measurement at the time of pH adjustment can be performed with a pH meter using a general glass electrode.
  • a general glass electrode Specifically, for example, trade name: MODEL (F-51) manufactured by HORIBA, Ltd. can be used.
  • (C) Synthesis step In the synthesis step, the concentration of the solid separated in the first washing step in an aqueous medium in the presence of an acid is such that the silicon atom concentration is 100 mmol / L or more and the aluminum atom concentration is 100 mmol / L or more.
  • Heat treatment is performed at In the conventional manufacturing method, aluminum silicate is grown in a tubular shape by performing heat treatment with a dilute solution. In such a conventional manufacturing method, there is a limit to improvement in productivity because the heat treatment is performed with a dilute solution.
  • an aluminum silicate having excellent metal ion adsorption ability and having a structure different from that of a tube by performing heat treatment under conditions where the concentration of silicon atoms and aluminum atoms exceeds a specific concentration as in the production method of the present invention. Can be manufactured with high productivity.
  • the silicon atoms and the aluminum atoms contained in the separated solid are adjusted so as to have a predetermined concentration.
  • the silicon atom concentration is 100 mmol / L or more and the aluminum atom concentration is 100 mmol / L or more.
  • the silicon atom concentration is 120 mmol / L or more and 2000 mmol / L or less and the aluminum atom concentration is 120 mmol / L or more and 2000 mmol / L or less, more preferably the silicon atom concentration is 150 mmol / L or more and 1500 mmol / L or less and the aluminum atom concentration is 150 mmol / L or more and 1500 mmol / L.
  • the productivity of aluminum silicate tends to decrease.
  • the silicon atom concentration and the aluminum atom concentration are the silicon atom concentration and the aluminum atom concentration after adjusting the pH to a predetermined range by adding an acidic compound described later.
  • the silicon atom concentration and the aluminum atom concentration are measured by an ordinary method using an ICP emission spectrometer (for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.).
  • a solvent may be added.
  • the solvent one that can easily be solvated with the raw material can be appropriately selected and used. Specifically, water, ethanol, etc. can be used, but the coexisting ions in the solution during the heat synthesis can be reduced. In view of ease of handling, it is preferable to use water.
  • the synthesis step at least one acidic compound is added before the heat treatment.
  • the pH after adding the acidic compound is not particularly limited. From the viewpoint of efficiently obtaining the desired aluminum silicate, the pH is preferably from 3 to less than 7, and more preferably from 3 to 5.
  • the acidic compound added in the synthesis step is not particularly limited, and may be an organic acid or an inorganic acid. Among these, it is preferable to use an inorganic acid. Specific examples of the inorganic acid include hydrochloric acid, perchloric acid, nitric acid and the like. Considering the reduction of coexisting ion species in the solution during the heat treatment described later, it is preferable to use an acidic compound that generates an anion similar to the anion contained in the used aluminum source.
  • the aluminum silicate which has a desired structure can be obtained by heat-processing.
  • the heating temperature is not particularly limited. From the viewpoint of efficiently obtaining the desired aluminum silicate, the temperature is preferably from 80 ° C to 160 ° C. There exists a tendency which can suppress that boehmite (aluminum hydroxide) precipitates that heating temperature is 160 degrees C or less. When the heating temperature is 80 ° C. or higher, the synthesis rate of the desired aluminum silicate is improved, and the desired aluminum silicate tends to be produced more efficiently.
  • the heating time is not particularly limited. From the viewpoint of more efficiently obtaining an aluminum silicate having a desired structure, it is preferably within 96 hours (4 days). When the heating time is 96 hours or less, the desired aluminum silicate can be produced more efficiently.
  • the second washing step only needs to be able to remove at least a part of anions other than silicate ions and cations other than aluminum ions, and may be the same operation as the first washing step before the synthesis step or a different operation. Good.
  • the second washing step is preferably performed so that the concentration of coexisting ions is not more than a predetermined concentration. Specifically, for example, when the solid separated product obtained in the second washing step is dispersed in pure water so as to have a concentration of 60 g / L, the electrical conductivity of the dispersion is 4.0 S / m.
  • the electrical conductivity of the dispersion is 4.0 S / m or less, it tends to be easy to obtain an aluminum silicate having a better metal ion adsorption ability.
  • the second washing step is performed using centrifugation, for example, it can be performed as follows.
  • the pH is adjusted to 5 to 10 by adding alkali or the like to the mixed solution.
  • the supernatant solution is discharged and the solid is separated as a gel-like precipitate.
  • the solid separated is then redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 10, preferably 8 to 10.
  • the alkali used for pH adjustment is not particularly limited.
  • sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and the standard rotor NA-16 of the same company, it can be set at 5 to 10 minutes at 3000 rpm (1450 G) or more at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of ease of handling, it is preferable to use water, and it is more preferable to use pure water.
  • pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the second washing step may be set according to the residual amount of coexisting ions, but is preferably 1 to 6 times, and if the washing is repeated about 3 times, the coexisting ions in aluminum silicate The remaining amount of is sufficiently reduced.
  • cleaning process it is preferable that especially the density
  • the chloride ion concentration is 100 mg / L or less and the sodium ion concentration is 100 mg / L or less, the adsorption ability can be further improved.
  • the chloride ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less.
  • the sodium ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less.
  • Chloride ion concentration and sodium ion concentration can be adjusted according to the number of treatments in the washing step and the type of alkali used for pH adjustment.
  • the chloride ion concentration and sodium ion concentration are measured under normal conditions by ion chromatography (for example, DX-320 and DX-100 manufactured by Dionex).
  • the concentration of the aluminum silicate dispersion is based on the mass of the solid obtained by drying the solid separated material at 110 ° C. for 24 hours.
  • the “dispersion after the second washing step” described here means a dispersion in which the volume is returned to the volume before the second washing step after the second washing step by using a solvent.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used. Specifically, water, ethanol, or the like can be used, but the residual amount of coexisting ions in the aluminum silicate can be used. From the viewpoint of reduction and ease of handling, it is preferable to use water.
  • the BET specific surface area of the aluminum silicate is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, discharging the supernatant solution, and gel precipitation)
  • the aluminum silicate remaining as a product can be redispersed in a solvent and adjusted to the volume before centrifugation by repeating the process once or a plurality of times.
  • the total pore volume of aluminum silicate is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, then discharging the supernatant solution to remove the gel
  • the aluminum silicate remaining as a precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or multiple times.
  • the average pore diameter of the aluminum silicate is determined by the treatment method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, then discharging the supernatant solution to remove the gel
  • the aluminum silicate remaining as a precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or multiple times.
  • the aluminum silicate of the first embodiment is useful as an adsorbent for metal ions. More specifically, nickel ions, copper ions, manganese ions and the like are effectively adsorbed.
  • the metal ion adsorbent according to the second embodiment of the present invention contains aluminum silicate as a component.
  • Aluminum silicate according to the second embodiment, the element ratio Si / Al of Si and Al is 0.3 to 1.0 molar ratio, has a peak at 3ppm near the 27 Al-NMR spectrum, 29
  • the Si-NMR spectrum has peaks around ⁇ 78 ppm and around ⁇ 85 ppm.
  • the element ratio Si / Al of Si and Al is 0.3 to 1.0 in terms of molar ratio from the viewpoint of improving the adsorption ability of metal ions, and 0.4 to 0.6 is preferable, and 0.45 to 0.55 is more preferable.
  • the Si / Al molar ratio is less than 0.3, the amount of Al that does not contribute to the improvement of the aluminum silicate adsorption capacity becomes excessive, and when it exceeds 1.0, the aluminum silicate adsorption capacity is improved.
  • the amount of Si that does not contribute tends to be excessive.
  • the element ratio Si / Al of Si and Al can be measured by an ordinary method using an ICP emission spectrometer (for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.).
  • ICP emission spectrometer for example, ICP emission spectrometer: P-4010 manufactured by Hitachi, Ltd.
  • the aluminum silicate according to the second embodiment has a peak in the vicinity of 3 ppm in the 27 Al-NMR spectrum.
  • the 27 Al-NMR measurement apparatus for example, AV400WB type manufactured by Bruker BioSpin can be used, and specific measurement conditions are as follows.
  • Resonance frequency 104MHz
  • Measuring method MAS (single pulse)
  • MAS rotation speed 10 kHz
  • Measurement area 52 kHz
  • Number of data points 4096 resolution (measurement area / number of data points): 12.7 Hz
  • Pulse width 3.0 ⁇ sec
  • Delay time 2 seconds
  • Chemical shift value standard 3.94 ppm of ⁇ -alumina window function: exponential function Line Broadening coefficient: 10 Hz
  • FIG. 2 shows a 27 Al-NMR spectrum of aluminum silicate according to Production Example 1 and Production Example 2 described later as an example of the aluminum silicate according to the second embodiment.
  • the aluminum silicate according to the second embodiment has a peak in the vicinity of 3 ppm in the 27 Al-NMR spectrum.
  • the peak around 3 ppm is estimated to be a peak derived from 6-coordinated Al.
  • the peak near 55 ppm is estimated to be a peak derived from tetracoordinated Al.
  • the area ratio of the peak near 55 pm to the peak near 3 ppm is preferably 25% or less, and preferably 20% or less. More preferably, it is more preferably 15% or less.
  • the specific aluminum silicate according to the present embodiment has an area ratio of a peak near 55 pm to a peak near 3 ppm in a 27 Al-NMR spectrum of 1% or more from the viewpoint of metal ion adsorption and metal ion selectivity. Preferably, it is 5% or more, more preferably 10% or more.
  • the aluminum silicate according to the second embodiment has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29 Si-NMR spectrum.
  • the 29 Si-NMR measurement apparatus for example, AV400WB type manufactured by Bruker BioSpin can be used, and specific measurement conditions are as follows.
  • Resonance frequency 79.5 MHz
  • Measuring method MAS (single pulse)
  • MAS rotation speed 6 kHz
  • Measurement area 24 kHz
  • Number of data points 2048 resolution (measurement area / number of data points): 5.8 Hz
  • Pulse width 4.7 ⁇ sec
  • Delay time 600 sec chemical shift value criterion: TMSP-d 4 (3- (trimethylsilyl) (2,2,3,3- 2 H 4) propionate) 1.52Ppm
  • the window function exponential function Line Broadening coefficient: 50 Hz
  • FIG. 3 shows 29 Si-NMR spectra of aluminum silicate according to Production Example 1 and Production Example 2 described later as an example of the aluminum silicate according to the second embodiment.
  • the aluminum silicate according to the second embodiment has peaks in the vicinity of ⁇ 78 ppm and in the vicinity of ⁇ 85 ppm in the 29 Si-NMR spectrum. Peak A appearing near ⁇ 78 ppm is considered to be derived from aluminum silicate having a crystal structure such as imogolite and allophanes, and peak B appearing near ⁇ 85 ppm is aluminum silicate or amorphous structure having a viscosity structure. Of aluminum silicate. Therefore, the aluminum silicate according to the second embodiment is presumed to be a mixture or a composite of an aluminum silicate having a crystal structure and an aluminum silicate having a viscosity structure or an amorphous structure.
  • the aluminum silicate according to the second embodiment has an area ratio (peak) between the peak A around ⁇ 78 ppm and the peak B around ⁇ 103.8 ppm in the 29 Si-NMR spectrum from the viewpoint of improving the adsorption ability of metal ions.
  • B / Peak A) is preferably from 0.4 to 9.0, more preferably from 1.5 to 9.0, still more preferably from 2.0 to 9.0. It is more preferably 0 to 7.0, further preferably 2.0 to 5.0, and particularly preferably 2.0 to 4.0.
  • the area of peak A near ⁇ 78 ppm is the area of the region surrounded by the straight line passing through ⁇ 81 ppm and the base line perpendicular to the chemical shift axis, and the area of peak B is orthogonal to the chemical shift axis.
  • require the area of each said peak with the analysis software integrated in the NMR measuring apparatus.
  • FIG. 4 and 5 show examples of transmission electron microscope (TEM) photographs of aluminum silicate according to the second embodiment.
  • the aluminum silicate shown in FIG. 4 is an aluminum silicate according to Production Example 1 described later.
  • the aluminum silicate shown in FIG. 5 is an aluminum silicate according to Production Example 2 described later.
  • the aluminum silicate according to Production Example 1 does not have a tubular product having a length of 50 nm or more when observed at a magnification of 100,000 with a transmission electron microscope (TEM).
  • the aluminum silicate according to Production Example 2 is a so-called imogolite having a tubular shape as shown in FIG.
  • Observation of aluminum silicate with a transmission electron microscope (TEM) is performed at an acceleration voltage of 100 kV.
  • TEM transmission electron microscope
  • a solution after heating before the second washing step (desalting and solid separation) in the manufacturing method described later is dropped on a support for preparing a TEM observation sample, and then dried to form a thin film.
  • an observation sample is prepared using an appropriately diluted solution after the heat treatment so that a sufficient contrast can be obtained.
  • an aluminum silicate in which a tubular product as shown in FIG. 4 is not observed is produced by performing a heat treatment of silicate ions and aluminum ions at a specific concentration or more.
  • FIG. 6 is a drawing schematically showing a so-called tubular imogolite, which is an example of an aluminum silicate according to the second embodiment.
  • the fiber structure tends to be formed by the tubular bodies 10a, and the outer wall (outer periphery) of the tubular body 10a forming the inner wall 20 in the tube of the tubular body 10a and the gap 30 between the tubular bodies 10a. Surface) can be used as an adsorption site for metal ions.
  • the length of the tubular body 10a in the tube portion length direction is, for example, 1 nm to 10 ⁇ m.
  • the tubular body 10a has a circular tubular shape, for example, and has an outer diameter of, for example, 1.5 to 3.0 nm and an inner diameter of, for example, 0.7 to 1.4 nm.
  • Powder X-ray diffraction is performed using CuK ⁇ rays as an X-ray source.
  • a powder X-ray diffractometer manufactured by Rigaku Corporation: Geigerflex RAD-2X (trade name) can be used.
  • the powder X-ray-diffraction spectrum of the aluminum silicate which concerns on the below-mentioned manufacture example 1 and manufacture example 2 is shown as an example of the aluminum silicate which concerns on 2nd embodiment.
  • precipitation of aluminum hydroxide can be suppressed by making the heating temperature at the time of heat processing into 160 degrees C or less.
  • content of aluminum hydroxide can be adjusted by adjusting pH at the time of the desalting process by centrifugation.
  • the aluminum silicate according to the second embodiment preferably has a BET specific surface area of 200 m 2 / g or more, more preferably 250 m 2 / g or more, from the viewpoint of improving the adsorption ability of metal ions. More preferably, it is 280 m 2 / g or more.
  • the upper limit of the BET specific surface area is not particularly limited, but a part of Si and Al in the aluminum silicate is bonded in the form of Si—O—Al, which contributes to the improvement of the metal ion adsorption capacity.
  • the BET specific surface area is preferably 1500 m 2 / g or less, more preferably 1200 m 2 / g or less, and still more preferably 1000 m 2 / g or less.
  • the BET specific surface area of aluminum silicate is measured from nitrogen adsorption capacity according to JIS Z 8830.
  • the evaluation apparatus for example, AUTOSORB-1 (trade name) manufactured by QUANTACHROME can be used.
  • AUTOSORB-1 trade name manufactured by QUANTACHROME
  • pretreatment for removing moisture by heating is first performed.
  • the measurement cell charged with 0.05 g of the measurement sample is depressurized to 10 Pa or less with a vacuum pump, heated at 110 ° C., held for 3 hours or more, and kept at a normal temperature while maintaining the depressurized state. Cool naturally to (25 ° C).
  • the evaluation temperature is 77K
  • the evaluation pressure range is measured as a relative pressure (equilibrium pressure with respect to saturated vapor pressure) of less than 1.
  • Aluminum silicate according to the second embodiment is preferably, 0.12 cm 3 / g or more that the total pore volume is 0.1 cm 3 / g or more More preferably, it is still more preferably 0.15 cm 3 / g or more.
  • the upper limit of the total pore volume is not particularly limited, but a part of Si and Al in the aluminum silicate bonds in the form of Si-O-Al, which contributes to the improvement of metal ion adsorption capacity.
  • the total pore volume is 1.5 m 2 / g or less, more preferably 1.2 m 2 / g or less, and 1.0 m 2 / g or less. Is more preferable.
  • the total pore volume of aluminum silicate is based on the BET specific surface area, and the gas adsorption amount closest to relative pressure 1 is converted to liquid among the data obtained when the relative pressure is 0.95 or more and less than 1. And ask.
  • the aluminum silicate according to the second embodiment preferably has an average pore diameter of 1.5 nm or more, more preferably 1.7 nm or more, from the viewpoint of improving the adsorption ability of metal ions. More preferably, it is 0.0 nm or more.
  • the upper limit of the total pore volume is preferably 50 nm or less, more preferably 20 nm or less, and further preferably 5.0 nm or less, from the viewpoint of improving the adsorption ability of metal ions.
  • the average pore diameter of aluminum silicate is determined on the basis of the BET specific surface area and the total pore volume, assuming that all the pores are composed of one cylindrical pore.
  • the aluminum silicate which is a component of the metal ion adsorbent according to the second embodiment of the present invention can be produced as follows.
  • the method for producing an aluminum silicate according to the second embodiment includes (a) a step of mixing a solution containing silicate ions and a solution containing aluminum ions to obtain a reaction product, and (b) the reaction product containing the reaction product. Desalting and solid separation, (c) heat-treating the solid separated in the step (b) in an aqueous medium in the presence of an acid, and (d) heating in the step (c). Steps for desalting and solid separation of the product obtained by the treatment are included, and other steps may be included if necessary.
  • metal ion adsorbent with excellent metal ion adsorption ability by desalting coexisting ions from a solution containing aluminum silicate which is a reaction product and then heat-treating in the presence of an acid. It can.
  • This can be considered as follows, for example.
  • An aluminum silicate having a regular structure is formed by heat-treating the aluminum silicate from which coexisting ions that inhibit the formation of the regular structure are removed in the presence of an acid. It can be considered that when aluminum silicate has a regular structure, the affinity for metal ions is improved and metal ions can be adsorbed efficiently.
  • Step of obtaining a reaction product In the step of obtaining a reaction product, a solution containing silicate ions and a solution containing aluminum ions are mixed to mix aluminum silicate as a reaction product and coexisting ions. Obtain a solution.
  • silicate ion and aluminum ion When synthesizing aluminum silicate, silicate ions and aluminum ions are required as raw materials.
  • the silicic acid source constituting the solution containing silicate ions (hereinafter also referred to as “silicate solution”) is not particularly limited as long as silicate ions are generated when solvated. Examples thereof include, but are not limited to, tetraalkoxysilanes such as sodium orthosilicate, sodium metasilicate, and tetraethoxysilane.
  • the aluminum source which comprises the solution containing aluminum ion will not be restrict
  • a material that can easily be solvated with the silicate source and the aluminum source as raw materials can be appropriately selected and used.
  • water, ethanol or the like can be used. It is preferable to use water from the viewpoint of reducing the coexisting ions in the solution during the heat treatment and ease of handling.
  • the silicon atom concentration of the silicic acid solution is not particularly limited. Preferably, it is 1 mmol / L to 1000 mmol / L. When the silicon atom concentration of the silicic acid solution is 1 mmol / L or more, productivity is improved and aluminum silicate can be produced efficiently. Moreover, productivity improves more according to the silicon atom concentration of a silicic acid solution as the silicon atom concentration of a silicic acid solution is 1000 mmol / L or less.
  • the aluminum atom concentration of the aluminum solution is not particularly limited. Preferably, it is 100 mmol / L to 1000 mmol / L. When the aluminum atom concentration of the aluminum solution is 100 mmol / L or more, productivity is improved, and aluminum silicate can be produced efficiently. Further, when the aluminum atom concentration of the aluminum solution is 1000 mmol / L or less, the productivity is further improved according to the aluminum atom concentration of the aluminum solution.
  • a solution containing silicate ions and a solution containing aluminum ions are mixed to produce an aluminum silicate containing coexisting ions as a reaction product, and then the aluminum silicate containing the coexisting ions is desalted and solid
  • a first cleaning step for separation is performed.
  • the first washing step at least a part of the coexisting ions is removed from the mixed solution to reduce the coexisting ion concentration in the mixed solution.
  • desalting and solid separation include anions other than silicate ions derived from a silicate source and an aluminum source (for example, chloride ions and nitrate ions) and cations other than aluminum ions (for example, sodium ions).
  • anions other than silicate ions derived from a silicate source and an aluminum source for example, chloride ions and nitrate ions
  • cations other than aluminum ions for example, sodium ions
  • the first washing step is preferably performed so that the concentration of coexisting ions is not more than a predetermined concentration.
  • the electrical conductivity of the dispersion is 4.0 S / m. It is preferable to carry out so that it is less than or equal to 1.0 mS / m or more and 3.0 S / m or less, more preferably 1.0 mS / m or more and 2.0 S / m or less. Is more preferable.
  • the electrical conductivity of the dispersion is 4.0 S / m or less, the desired aluminum silicate tends to be more easily formed in the synthesis step.
  • the electrical conductivity is measured at normal temperature (25 ° C.) using FORI 55 manufactured by HORIBA Co., Ltd. and 9382-10D, a general electrical conductivity cell manufactured by HORIBA.
  • the first washing step includes a step of dispersing the aluminum silicate in an aqueous medium to obtain a dispersion, a step of adjusting the pH of the dispersion to 5 to 7, and a step of precipitating the aluminum silicate. It is preferable to include.
  • cleaning process using centrifugation it can carry out as follows.
  • the pH is adjusted to 5 to 8 by adding alkali or the like to the mixed solution. After centrifuging the pH-adjusted solution, the supernatant solution is discharged and the solid is separated as a gel-like precipitate. The separated solid is redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 8, but preferably 5.5 to 6.8, and more preferably 5.8 to 6.5.
  • the alkali used for pH adjustment is not particularly limited. For example, sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and its standard rotor NA-16, it can be set at 3000 rpm (1450 G) or more for 5 to 10 minutes at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of the reduction of coexisting ions and ease of handling, water is preferably used, and pure water is more preferably used. It should be noted that pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the first washing step may be appropriately set according to the remaining amount of coexisting ions. For example, it can be 1 to 6 times. If the washing is repeated about three times, the residual amount of coexisting ions is reduced to such an extent that does not affect the synthesis of the desired aluminum silicate.
  • PH measurement at the time of pH adjustment can be performed with a pH meter using a general glass electrode.
  • a general glass electrode Specifically, for example, trade name: MODEL (F-51) manufactured by HORIBA, Ltd. can be used.
  • (C) Synthesis step In the synthesis step, the solid separated in the first washing step is heat-treated in an aqueous medium in the presence of an acid.
  • An aluminum silicate having a regular structure can be formed by heat-treating a solution (dispersion) containing aluminum silicate with reduced coexisting ions in the first cleaning step in the presence of an acid. it can.
  • the synthesis step may be performed as a diluted solution by appropriately diluting the solid separated in the first washing step, or may be carried out as a high-concentration solution after solid separation in the first washing step.
  • an aluminum silicate having a structure in which a regular structure extends in a tubular shape hereinafter also referred to as “first aluminum silicate”
  • first aluminum silicate aluminum silicate having a structure in which a regular structure extends in a tubular shape
  • second aluminum silicate an aluminum silicate having a viscosity structure and an amorphous structure in addition to a regular structure.
  • both the first and second aluminum silicates have a specific regular structure, they exhibit excellent metal ion adsorption ability.
  • the silicon atom concentration can be 20 mmol / L or less and the aluminum atom concentration can be 60 mmol / L or less.
  • the silicon atom concentration is 0.1 mmol / L or more and 10 mmol / L or less
  • the aluminum atom concentration is 0.1 mmol / L or more and 34 mmol / L or less
  • the silicon atom concentration is 0.00.
  • the first aluminum silicate can be efficiently produced.
  • silicon atom concentration can be 100 mmol / L or more and aluminum atom concentration can be 100 mmol / L or more, for example.
  • the silicon atom concentration is preferably 120 mmol / L or more and 2000 mmol / L or less
  • the aluminum atom concentration is preferably 120 mmol / L or more and 2000 mmol / L or less
  • the silicon atom concentration is 150 mmol / L or more and 1500 mmol / L.
  • the aluminum atom concentration is not less than 150 mmol / L and not more than 1500 mmol / L.
  • the silicon atom concentration and the aluminum atom concentration are the silicon atom concentration and the aluminum atom concentration after adjusting the pH to a predetermined range by adding an acidic compound described later. Further, the silicon atom concentration and the aluminum atom concentration are measured using an ICP emission spectrometer (for example, ICP emission spectrometer P-4010 manufactured by Hitachi, Ltd.).
  • a solvent may be added.
  • the solvent one that can easily be solvated with the raw material can be appropriately selected and used. Specifically, water, ethanol, etc. can be used, but the coexisting ions in the solution during the heat treatment can be reduced. In view of ease of handling, it is preferable to use water.
  • the synthesis step at least one acidic compound is added before the heat treatment.
  • the pH after adding the acidic compound is not particularly limited. From the viewpoint of efficiently obtaining the desired aluminum silicate, the pH is preferably from 3 to less than 7, and more preferably from 3 to 5.
  • the acidic compound added in the synthesis step is not particularly limited, and may be an organic acid or an inorganic acid. Among these, it is preferable to use an inorganic acid. Specific examples of the inorganic acid include hydrochloric acid, perchloric acid, nitric acid and the like. Considering the reduction of coexisting ion species in the solution during the subsequent heat treatment, it is preferable to use an acidic compound that generates an anion similar to the anion contained in the used aluminum source.
  • the aluminum silicate which has a desired structure can be obtained by heat-processing.
  • the heating temperature is not particularly limited. From the viewpoint of efficiently obtaining the desired aluminum silicate, the temperature is preferably from 80 ° C to 160 ° C. There exists a tendency which can suppress that boehmite (aluminum hydroxide) precipitates that heating temperature is 160 degrees C or less. When the heating temperature is 80 ° C. or higher, the synthesis rate of the desired aluminum silicate is improved, and the desired aluminum silicate tends to be produced more efficiently.
  • the heating time is not particularly limited. From the viewpoint of more efficiently obtaining an aluminum silicate having a desired structure, it is preferably within 96 hours (4 days). When the heating time is 96 hours or less, the desired aluminum silicate can be produced more efficiently.
  • a metal ion adsorbent having excellent metal ion adsorption ability is obtained by desalting and solid separation by the second washing step in which at least a part of the coexisting ions is removed from the aluminum silicate obtained in the synthesis step. Can be considered.
  • the second washing step only needs to be able to remove at least a part of anions other than silicate ions and cations other than aluminum ions, and may be the same operation as the first washing step before the synthesis step or a different operation. Good.
  • the second washing step is preferably performed so that the concentration of coexisting ions is not more than a predetermined concentration. Specifically, for example, when the solid separated product obtained in the second washing step is dispersed in pure water so as to have a concentration of 60 g / L, the electrical conductivity of the dispersion is 4.0 S / m.
  • the electrical conductivity of the dispersion is 4.0 S / m or less, it tends to be easy to obtain an aluminum silicate having a better metal ion adsorption ability.
  • the second washing step is performed using centrifugation, for example, it can be performed as follows.
  • the pH is adjusted to 5 to 10 by adding alkali or the like to the mixed solution.
  • the supernatant solution is discharged and the solid is separated as a gel-like precipitate.
  • the solid separated is then redispersed in a solvent. In that case, it is preferable to return to the volume before centrifugation.
  • the concentration of the coexisting ions can be reduced to a predetermined concentration or less by repeating the operations of desalting and solid separation by centrifugal separation of the redispersed dispersion in the same manner.
  • the pH is adjusted to, for example, 5 to 10, preferably 8 to 10.
  • the alkali used for pH adjustment is not particularly limited.
  • sodium hydroxide and ammonia are preferable.
  • the centrifugation conditions are appropriately selected according to the production scale and the container used. For example, it can be 1 to 30 minutes at 1200 G or more at room temperature. Specifically, for example, in the case of using SUPREMA23 manufactured by TOMY as a centrifugal separator and its standard rotor NA-16, it can be set at 3000 rpm (1450 G) or more for 5 to 10 minutes at room temperature.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used.
  • water, ethanol, or the like can be used. From the viewpoint of ease of handling, it is preferable to use water, and it is more preferable to use pure water.
  • pH adjustment is preferably omitted when repeated washing is performed a plurality of times.
  • the number of treatments for desalting and solid separation in the second washing step may be set according to the residual amount of coexisting ions, but is preferably 1 to 6 times, and if the washing is repeated about 3 times, The remaining amount of is sufficiently reduced.
  • cleaning process it is preferable that especially the density
  • the chloride ion concentration is 100 mg / L or less and the sodium ion concentration is 100 mg / L or less, the adsorption ability can be further improved.
  • the chloride ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less.
  • the sodium ion concentration is more preferably 50 mg / L or less, and still more preferably 10 mg / L or less.
  • Chloride ion concentration and sodium ion concentration can be adjusted according to the number of treatments in the washing step and the type of alkali used for pH adjustment.
  • the chloride ion concentration and sodium ion concentration are measured under normal conditions by ion chromatography (for example, DX-320 and DX-100 manufactured by Dionex).
  • the concentration of the aluminum silicate dispersion is based on the mass of the solid obtained by drying the solid separated material at 110 ° C. for 24 hours.
  • the “dispersion after the second washing step” described here means a dispersion in which the volume is returned to the volume before the second washing step after the second washing step by using a solvent.
  • a solvent that can easily be solvated with the raw material can be appropriately selected and used. Specifically, water, ethanol, or the like can be used. From the viewpoint of reduction and ease of handling, it is preferable to use water.
  • the BET specific surface area of the aluminum silicate according to the present invention is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, and then discharging the supernatant solution.
  • the aluminum silicate remaining as a gel-like precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or a plurality of times.
  • the total pore volume of aluminum silicate is determined by the processing method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, then discharging the supernatant solution to remove the gel
  • the aluminum silicate remaining as a precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or multiple times.
  • the average pore diameter of the aluminum silicate is determined by the treatment method of the second washing step (for example, adding alkali to the synthesis solution to adjust the pH to 5-10, centrifuging, then discharging the supernatant solution to remove the gel
  • the aluminum silicate remaining as a precipitate is redispersed in a solvent, and the process of returning to the volume before centrifugation is repeated once or multiple times.
  • the metal ion adsorbent according to the second embodiment is composed of the aluminum silicate, and is useful as an adsorbent for metal ions. More specifically, the honeycomb-shaped substrate or porous substrate having liquid permeability is coated with a metal ion adsorbent and used as a filter, and the surface of a granular or spherical substrate is coated with a metal ion adsorbent. It can be used by filling the base material in a container and using the metal ion adsorbent itself.
  • the base material mentioned above is not specifically limited, Natural materials, such as a metal, a ceramic, a synthetic resin hardened
  • metal ions nickel ions, copper ions, manganese ions, etc. are effectively adsorbed.
  • sample A The gel precipitate obtained after the third desalting of the desalting treatment was dried at 60 ° C. for 16 hours to obtain 30 g of powder. This powder was designated as sample A.
  • As the evaluation device AUTASORB-1 (trade name) manufactured by QUANTACHROME was used. When performing these measurements, after pre-treatment of the sample described later, the evaluation temperature is 77K, and the evaluation pressure range is less than 1 in relative pressure (equilibrium pressure with respect to the saturated vapor pressure).
  • the measurement cell charged with 0.05 g of sample A was automatically degassed and heated with a vacuum pump.
  • the detailed conditions of this treatment were set such that the pressure was reduced to 10 Pa or less, heated at 110 ° C., held for 3 hours or more, and then naturally cooled to room temperature (25 ° C.) while maintaining the reduced pressure.
  • the BET specific surface area of Sample A was 363 m 2 / g, the total pore volume was 0.22 cm 3 / g, and the average pore diameter was 2.4 nm.
  • FIG. 2 shows the 27 Al-NMR spectrum of Sample A. As shown in FIG. 2, it had a peak around 3 ppm. A slight peak was observed around 55 ppm. The area ratio of the peak near 55 ppm to the peak near 3 ppm was 15%.
  • Fig. 3 shows the 29Si-NMR spectrum of Sample A. As shown in FIG. 3, there were peaks at around -78 ppm and around -85 ppm. The peak areas around ⁇ 78 ppm and ⁇ 85 ppm were measured by the above method. As a result, when the area of the peak A at ⁇ 78 ppm was 1.00, the area of the peak B at ⁇ 85 ppm was 2.61.
  • FIG. 4 shows a transmission electron microscope (TEM) photograph of sample A observed at a magnification of 100,000.
  • the TEM observation was performed using a transmission electron microscope (H-7100FA, manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 100 kV.
  • a sample A to be observed with TEM was prepared as follows. That is, the solution after heating (aluminum silicate concentration of 47 g / L) before the final desalting treatment process was diluted 10 times with pure water and subjected to ultrasonic irradiation for 5 minutes. It was prepared by dropping it onto a support and then drying it naturally to form a thin film. As shown in FIG. 4, there is no tubular object having a length of 50 nm or more.
  • Metal ion adsorption capacity was evaluated by ICP emission spectroscopic analysis (ICP emission spectrophotometer: P-4010 (manufactured by Hitachi, Ltd.)).
  • ICP emission spectrophotometer P-4010 (manufactured by Hitachi, Ltd.)
  • a 100 ppm metal ion solution was prepared using each metal sulfate and pure water. It added so that the sample A might be 1.0 mass% with respect to the prepared solution, and it left still, after mixing sufficiently. Then, each metal ion concentration before and after the addition of sample A was measured by ICP emission spectroscopic analysis.
  • the concentration after addition of sample A was less than 5 ppm for Ni 2+ and 10 ppm for Mn 2+ .
  • Sample B was commercially available activated carbon (manufactured by Wako Pure Chemical Industries, Ltd., activated carbon, crushed, 2 mm to 5 mm). Regarding the metal ion adsorption capacity, the concentration after addition of Sample B was 50 ppm for Ni 2+ and 60 ppm for Mn 2+ .
  • Sample C was a commercially available silica gel (manufactured by Wako Pure Chemical Industries, Ltd., small granular (white)). Regarding the metal ion adsorption capacity, the concentration after addition of Sample C was 100 ppm for Ni 2+ and 100 ppm for Mn 2+ .
  • Sample D was commercially available zeolite 4A (manufactured by Wako Pure Chemical Industries, Ltd., Molecular Sieves 4A). Regarding the metal ion adsorption capacity, the concentration after addition of Sample D was 30 ppm for Ni 2+ and 10 ppm for Mn 2+ . The Mn 2+ solution to which zeolite 4A was added turned brown and turbid when left standing.
  • centrifugal separation was performed for 5 minutes at a rotation speed of 3,000 rpm using a TOMY Corporation: Suprema 23 and standard rotor NA-16 as a centrifugal separator. After centrifugation, the supernatant solution was discharged, the gel precipitate was redispersed in pure water, and returned to the volume before centrifugation. Such desalting treatment by centrifugation was performed three times.
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was adjusted so as to have a concentration of 60 g / L, and it was used at normal temperature using FORI 55: F-55 and conductivity cell: 9382-10D.
  • the electrical conductivity was measured at 25 ° C. and found to be 1.3 S / m.
  • Pure water was added to the gel-like precipitate obtained after the third desalting of the desalting treatment to make the volume 12 L.
  • the silicon atom concentration and the aluminum atom concentration in the solution at this time were measured using an ICP emission spectrometer: P-4010 (manufactured by Hitachi, Ltd.), the silicon atom concentration was 2 mmol / L and the aluminum atom concentration was 4 mmol. / L.
  • the solution was then placed in a dryer and heated at 98 ° C. for 96 hours (4 days).
  • the gel-like precipitate obtained after the third desalting of the desalting treatment was adjusted so as to have a concentration of 60 g / L, and it was used at normal temperature using FORI 55: F-55 and conductivity cell: 9382-10D.
  • the electric conductivity was measured at 25 ° C., it was 0.6 S / m.
  • Powder X-ray diffraction of Sample E was performed in the same manner as in Production Example 1.
  • FIG. 2 shows the 27 Al-NMR spectrum of Sample E. As shown in FIG. 2, it had a peak around 3 ppm. A slight peak was observed around 55 ppm. The area ratio of the peak around 55 ppm to the peak around 3 ppm was 4%.
  • FIG. 3 shows the 29 Si-NMR spectrum of Sample E. As shown in FIG. 3, there were peaks near ⁇ 78 ppm and ⁇ 85 ppm. The peak areas around ⁇ 78 ppm and ⁇ 85 ppm were measured by the above method. As a result, when the area of peak A near ⁇ 78 ppm was 1.00, the area of peak B near ⁇ 85 ppm was 0.44.
  • FIG. 5 shows a transmission electron microscope (TEM) photograph of Sample E observed at a magnification of 100,000 by the same method as in Example 1.
  • TEM transmission electron microscope
  • Metal ion adsorption capacity evaluation 1 Using the sample A produced in Production Example 1, the metal ion adsorption ability was evaluated by the method described in Production Example 1 except that the amount of Sample A added was changed as shown in the following table. The results are shown in the table below.
  • Metal ion adsorption capacity evaluation 2 Using the sample A prepared in Production Example 1, the metal ion adsorption ability was evaluated by the method described in Production Example 1 except that the metal ion species was changed to Cu 2+ and the metal ion adjustment concentration was changed to 400 ppm. The pH at this time was 5.1. The concentration after addition of Sample A was 160 ppm for Cu 2+ .
  • Japanese Patent Application 2011-054787, Japanese Patent Application 2011-054788, Japanese Patent Application 2011-054857, and Japanese Patent Application 2011-054858 are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

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PCT/JP2011/078349 2011-03-11 2011-12-07 アルミニウムケイ酸塩、金属イオン吸着剤及びそれらの製造方法 WO2012124222A1 (ja)

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US14/004,581 US9782749B2 (en) 2011-03-11 2011-12-07 Aluminum silicate, metal ion adsorbent, and method for producing same
EP11861291.0A EP2684847B1 (en) 2011-03-11 2011-12-07 Aluminum silicate, metal ion adsorbent, and method for producing same
KR1020137025289A KR101907048B1 (ko) 2011-03-11 2011-12-07 알루미늄 규산염, 금속 이온 흡착제 및 이들의 제조 방법
JP2013504521A JP5958461B2 (ja) 2011-03-11 2011-12-07 アルミニウムケイ酸塩、金属イオン吸着剤及びそれらの製造方法
CN201180069225.7A CN103635426B (zh) 2011-03-11 2011-12-07 铝硅酸盐、金属离子吸附剂及它们的制造方法

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KR20180014733A (ko) 2015-06-04 2018-02-09 도아고세이가부시키가이샤 리튬 이온 2 차 전지용 이온 포착제, 전해액, 세퍼레이터 및 리튬 이온 2 차 전지
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JP2021065832A (ja) * 2019-10-23 2021-04-30 国立研究開発法人産業技術総合研究所 アルミニウムケイ酸塩又はアルミニウム水和物を含む有害物質吸着剤、アルミニウム水和物、アルミニウムケイ酸塩又はアルミニウム水和物の製造方法、及び有害物質の除去方法

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JP7010274B2 (ja) 2019-10-23 2022-01-26 国立研究開発法人産業技術総合研究所 アルミニウムケイ酸塩又はアルミニウム水和物を含む有害物質吸着剤、アルミニウム水和物、アルミニウムケイ酸塩又はアルミニウム水和物の製造方法、及び有害物質の除去方法

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US9782749B2 (en) 2017-10-10
TW201236975A (en) 2012-09-16
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EP2684847A1 (en) 2014-01-15
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